Hydrothermally crystallized Sr-containing bioactive glass film and its cytocompatibility

Sr-containing bioactive glass film with the Sr/(Ca+Sr) atomic ratio of 20% was sol-gel coated on titanium substrate, followed by hydrothermal treatment in a mixed phosphate solution (8 mM CaHPO₄ and 2 mM SrHPO₄) and other media at 120 or 140 °C. X-ray diffraction (XRD) analysis confirms amorphous nature of the gel powder calcined at 610 °C, but small peaks of Ca_1.8Sr_0.2SiO₄ or Ca_1.5Sr_0.5SiO₄ are also present. The absorption bands of Si-O-Si, PO₄ and OH groups and a weak absorption band of NO₃ groups appear in FT-IR spectrum of the calcined gel powder. Hydroxyapatite (HA) is detected for the hydrothermally treated sample by XRD and Raman analyses. Sr-containing HA nanocrystallites are formed on the film through a dissolution and precipitation mechanism in the hydrothermal treatment. The appearant bonding strength is 21±1 MPa for the both samples. In the test with MC3T3-E1 cells, the two coated samples exhibit larger viability, higher ALP levels and better cell morphology than the polished sample.     

溶胶-凝胶法CaO-P2O5-SiO2系生物玻璃的制备及机理探讨

以正硅酸乙酯[Si(OC2H5)4]、四水硝酸钙[Ca(NO3)2*4H2O]等作为前驱体,采用溶胶-凝胶工艺制备CaO-P2O5-SiO2系生物活性玻璃,把制备的样品放在模拟体液中浸泡一段时间后取出,以X-射线衍射、红外光谱等手段对其作物相分析,确定在玻璃的表面有羟基磷灰石相生成,同时对其形成机理做了进一步探讨.     

Formation of apatite nano-needles on novel gel derived SiO2-P2O5-CaO-SrO-Ag2O bioactive glasses

A novel SiO₂-P₂O₅-CaO-SrO-Ag₂O bioactive glass containing from 0 to 10 mol% Ag₂O was produced via the sol-gel method. The influence of silver content on in vitro hydroxyapatite (HA) formation, antibacterial and cell viability properties were investigated. The apatite shape and structure were evaluated by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction analysis (XRD). The results demonstrated that the rate of formation of crystalline HA on SiO₂-P₂O₅-CaO-SrO-Ag₂O bioactive glass containing 5% Ag₂O (BG-5A) was higher in comparison with other specimens. Formation of apatite nano-needles on the SiO₂-P₂O₅-CaO-SrO-5%Ag₂O surface in vitro, after 3 days soaking in SBF solution, demonstrated high bioactivity. The alkaline phosphatase (ALP) and 3-(4,5dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay evaluation methods illustrated that the presence of low silver (3% and 5% Ag₂O) had stimulating effect on promoting both differentiation and proliferation of G292 osteoblastic cells. Finally, results offer that specimen BG-5A is well candidate for bone tissue application with considerable high antibacterial potential, bioactivity and optimal cell viability.     

Structural and microstructural comparison of bioactive melt-derived and gel-derived glasses from CaO-SiO2 binary system

Two glasses from CaO-SiO₂ binary system were obtained by sol-gel and melting techniques. The effect of two different glass obtaining methods was investigated using X-ray diffraction, FTIR, Raman and ²⁹Si MAS NMR spectroscopic methods. The measurements revealed significant differences in the glasses structure. Although both glasses were fully amorphous, the gel-derived glass had a more polymerized structure compared to the melt-derived one. The studied glasses were characterized by BET analysis to provide information about specific surface area of the obtained materials. Apart from microstructural evaluation, thermal properties and in vitro bioactivity study of all glasses were conducted to demonstrate differences in performance of the samples. The formation process of hydroxycarbonate apatite (HCA) layer was investigated using inductively coupled plasma mass spectrometry (ICP-MS) and structural studies.     

Electrochemical study of the in vitro degradation of plasma-sprayed hydroxyapatite/bioactive glass composite coatings after heat treatment

Hydroxyapatite (HA)-coated implants plasma-sprayed on metallic substrates have been widely used in load-bearing applications. In the present work, the in vitro behaviors of bioactive glass-containing HA coatings with post-deposition heat treatment in a simulated body fluid has been performed by means of electrochemical techniques. Annealing of the coatings in air at 650 °C led to recrystallization of amorphous calcium phosphate and effectively increased the conversion of non-apatite phases into apatite. The heat treatment also resulted in a reduction of layer defects associated with plasma-sprayed coatings without adversely affecting bond strength of the coatings. Moreover, the heat-treated coatings significantly increased the corrosion potential and polarization resistance value by approximately two times as compared to untreated samples. Improved corrosion resistance could be attributed to reduction of layer defects and enhancement of coating crystallinity.     

Fabrication and characterization of ZnO modified bioactive glass nanoparticles

Bioactive glass nanoparticles in the system (SiO₂-CaO-P₂O₅-ZnO) were synthesized following the sol-gel technique. The prepared glass nanoparticles of 1, 3 and 5 wt% of ZnO (coded: GZ1, GZ3 and GZ5, respectively) were characterized by TEM, FTIR, XRF, TGA and DSC. All glass powders had particle sizes less than 100 nm. Textural analysis revealed that for GZ1, GZ3 and GZ5, the average pore diameters, measured by the high-speed gas sorption analyzer, were 15.9, 15.4 and 15.2 nm, respectively, while the average pore diameters measured by the mercury intrusion porosimetry were 47, 50 and 63 nm, respectively. All glass powders were highly porous (75, 76 and 75%) with surface areas of 233, 94 and 118 m²/g for GZ1, GZ3 and GZ5, respectively. All glass powders induced an apatite layer on their surfaces upon immersion in simulated body fluid (SBF) as verified by SEM and TF-XRD.     

Apatite formation on melt-derived bioactive glass powder based on SiO2-CaO-Na2O-P2O5 system

The higher melting temperature and longer soaking time during conventional glass melting route promoted the search for alternative in developing new bioactive glass (BG) composition with improved in fabrication temperature and melting time. The current project involved fabrication of new BG compositions based on SiO₂-CaO-Na₂O-P₂O₅ system via melt derived route. It was confirmed that all bioactive glass composition can be melted at temperature lower than 1400 °C. Formation of Si-O-Si (tetrahedral) functional group highlighted that silicate based glass was established as detected by Fourier transform infrared spectroscope (FTIR). BG bioactivity was performed by incubating the BG powder in Tris-buffer solution (pH 8) for 7, 14 and 21 days. In vitro test confirmed the apatite formation on the bioactive glass surface upon soaking in Tris-buffer solution with characteristic of carbonate group (C-O) and P-O band noticed from FTIR and present of crystalline peak observed in X-ray diffraction (XRD). Morphology of apatite formation on BG surface was observed using scanning electron microscope (SEM).     

Synthesis, characterization and microbiological response of silver doped bioactive glass nanoparticles

Glass nanoparticles containing 1, 3, 5, and 10 wt% of Ag₂O (coded; GAg1%, GAg3%, GAg5%, and GAg10%, respectively) were synthesized through a quick alkali mediated sol-gel method and were characterized by TEM, XRF, FT-IR, XRD, TGA, and DSC. Thermal analysis showed that all organic and inorganic by-products were completely decomposed before 700 °C and, hence, all glass samples were stabilized at this temperature. XRD confirmed the amorphous nature of all glasses after stabilization. TEM micrographs showed that the average particle sizes of all samples were less than 100 nm in diameter and the XRF showed that the compositions of the obtained glasses were almost consistent with the designed ones. The samples GAg1%, GAg3%, GAg5%, and GAg10%, showed average pore diameters of 19.85, 18.22, 13.32, and 19.62 nm and specific surface areas of 73.18, 100.38, 192.6, and 55.7 m²/g, respectively. In addition, their porosity% was 76.53, 83.20, 77.97, and 79.61%, respectively. The FT-IR spectra of all glasses showed bands located in the range of 1000-1200, 725-800, and 450-480 cm⁻¹ that correspond to the Si-O-Si asymmetric stretching vibration, the Si-O-Si symmetric stretching vibration, and the Si-O-Si bending mode, respectively. Finally, all samples had an anti-bacterial effect against different types of bacteria and the extraction of silver ions from them followed a diffusion-controlled mechanism, which could demonstrate their ability to treat bone infection.     

Mechanical properties,bioactivity and cell behavior of barium-containing calcium-phospho-alumino-borosilicate glass

In this study, the effect of replacing CaO by BaO on mechanical properties, bioactivity, and cell adhesion of SiO₂–B₂O₃–Al₂O₃–P₂O₅–CaO–Na₂O based glass was investigated. Mechanical characterization, depth-sensing nano-indentation, and surface micro-indentation techniques were employed to determine the fracture toughness (K_IC). The surface was photographed after micro-indentation effect using scanning electron microscopy. In vitro responses of the compounds of tris-buffered SBF solution were studied from different points of view: (i) morphology and elemental surface analysis using field emission electron microscopy equipped with energy dispersive spectroscopy; (ii) change in bonds using Raman spectroscopy; and (iii) ICP method for detecting the change in ion chemistry of SBF solution. The cell adhesion behavior was qualitatively evaluated by examining the morphology and attachment of mouse fibroblastic cells to the surface of the glasses. The results demonstrated that with the replacement of barium oxide, the hardness of the base glass increased, while the level of fracture toughness was maintained. In addition, in vitro bioactivity of barium oxide-containing glass was reduced compared to the base glass. However, structural dissolution and formation of calcium phosphate layers on their surfaces were also confirmed. The results showed that BaO-incorporated glasses had adequate cell propagation and proliferation, hence enjoying appropriate biocompatibility for use in coating applications.     

In vivo toxicological evaluation of barium-doped bioactive glass in rats

Bioactive glasses (BGs) are inorganic biomaterials with several FDA-approved marketed products, mainly for orthopedic and dental applications. However, in the last few decades, the soft tissue regenerative potential of BGs has also been established preclinically, and its clinical translation requires elaborate in vivo toxicity studies for future biomedical applications. Thus, in the present study, we evaluated the comparative acute and sub-acute toxicity of orally administered barium-doped BG (BaBG) with 45S5 in rats. The lethal dose (LD₅₀) of BaBG and 45S5 was more than 2000 mg/kg body weight (b.w.), with no mortality at the highest dose tested. The oral acute toxicity study was performed at doses of 300 and 2000 mg/kg b.w. according to OECD 423. The organ coefficients of vital organs and histological analysis affirmed the safety profile of BaBG. Moreover, various biochemical indices like alanine aminotransferase (ALT), aspartate aminotransferase (AST), alkaline phosphatase (ALP), creatinine, and CK-MB confirmed that BaBG did not cause organ toxicity at all doses tested. Similarly, the repeated dose 28-days sub-acute toxicity study was performed according to OECD 407 at doses 50, 500, and 1000 mg/kg b.w. There was no alteration in the hematological parameters, which ascertains that BaBG had no toxic effects on the hematopoietic centers like 45S5. Furthermore, there was no observed neuro-behavioral toxicity of 45S5 and BaBG. Thus, these findings confirm that BaBG is non-toxic and can be used for therapeutic applications in different disease models.     

Electrophoretic deposition of bioactive glass nanopowders on magnesium based alloy for biomedical applications

To slow down the initial biodegradation rate of magnesium (Mg) alloy, crystalline nano-sized bioactive glass coating was used to deposit on micro-arc oxidized AZ91 samples via electrophoretic deposition (EPD). Zeta potential and conductivity of the bioactive glass suspension were characterized at various pH values to identify the most stable dispersion conditions. The bone-bonding properties of bioactive glass coated samples were evaluated in terms of apatite-forming ability during the immersion in simulated body fluid (SBF) solution. Results revealed that the ability to form a bioactive glass coating via EPD was influenced by the degree of its crystalline phase composition. Moreover, the potentiodynamic polarization tests recorded significant drops in corrosion current density and corrosion rate of the coated samples which implies a good level of corrosion protective behavior. These preliminary results show that this process will enable the development of Mg implants in the later stage of bone healing.     

Effect of B2O3 on the structural and in vitro biological assessment of mesoporous bioactive glass nanospheres

In this paper, the boron-containing mesoporous bioactive glass (MBG) nanospheres have been successfully synthesized by modified sol-gel method assisted by surfactant, and the effect of boron substitution on structure and bioactivity was evaluated by combining experiments and ab initio molecular dynamics (AIMD) simulations. All of the samples exhibit regularly uniform mesoporous spherical microstructure with an average size of about 60 nm, and the boron-containing MBGs show higher specific surface area with the value up to 416.20 m²/g. The simulated body fluid (SBF) immersion test confirms that the deposited hydroxyapatite (HA) evidently increases with the increasing of boron content, indicating that the biological behavior has been significantly improved resulting from incorporation of boron. Additionally, our results also reveal that B₂O₃ substitution has positive impact on cell proliferation of human periodontal ligament cells (hPDLCs) at lower extracted concentration. Furthermore, AIMD simulation is employed to understand the relationship between structural changes and in vitro bioactivity in terms of structural information, especially the boron coordination number. The results illustrate that the boron-containing MBG nanospheres with excellent bioactivity are great potential for biomedical applications.     

In vitro evaluation and mechanical studies of MgO added borophosphate glasses for biomedical applications

The objective of current research is to evaluate the bioactive and tribological properties of the MgO doped borophosphate glass system. The glass system constituted of 40% B₂O₃ - (20-x) % CaO – 25% Li₂O – 15% P₂O₅ – x % MgO (mol%), x = 0, 0.5, 01, 02, 03 and synthesized using the melt quench technique. In-vitro bioactivity was determined using simulated body fluid (SBF) at 37 °C with time intervals of 7, 14 and 21 days. Hydroxyapatite (HA) layer formation was assessed using characterization techniques like XRD, FTIR and FESEM-EDS for structural, functional and morphological analysis respectively. The effect of MgO content on microhardness and tribological properties was studied by making cylindrical shaped glass samples. MTT assay was performed for various doses (62.5–1000 μg/ml) of glass dilutions using MG-63 cell line. In-vitro bioactivity showed higher Ca/P ratio with increase in MgO content after 21 days of immersion. MgO content seemed to promote degradation of glass due to formation of open structure in glass network. Borophosphate glass having 3% MgO exhibited the highest hardness value of 5.79(±0.08) GPa with minimum specific wear rate of 1.86 × 10^?11 and 1.38 × 10^?11 m³/Nm at a load of 15 N and 20 N respectively. MTT assay demonstrated the non-toxic behaviour of glass samples even at a higher dose level of 1000 μg/ml which confirmed its biocompatible behaviour. The study suggests that produced MgO doped borophosphate glass exhibits essential characteristics of bioactive materials and hence could be effective in bone filling and wound healing applications.     

Fabrication and in vitro characterization of antibacterial magneto-luminescent core-shell bioactive glass nanoparticles

When nanomaterials with antibacterial properties were sent to the infected area, it was predicted that infection and related complications could be prevented. The nanoparticles can be designed to possess magnetic and luminescence (magneto-luminescent) properties to be effectively targeted and localized at the infection foci without dispersing into the body. Simultaneously, the magneto-luminescent characteristic of particles allows visualization and confirmation of localized particles at the desired area. In this regard, there are no studies on the use of antibacterial magneto-luminescent bioactive glass for orthopedic applications and the treatment of orthopedic device-related infections. In this study, antibacterial magneto-luminescent 58S bioactive glasses were synthesized by the modified Stöber using coupled with a layer-by-layer assembly approach to possess core/shell particle morphology. SPION/Bioactive glass nanoparticles had an average size of 50 nm and displayed superparamagnetic behavior. While the saturation magnetization value (σ_s) of the undoped 58S sample was 25.32 emu/g, that of the co-doped sample (2% Eu, 2% Zn) was 21.74 emu/g; this showed that the doping slightly reduced the magnetization value. Europium (Eu) doping of SPION/Bioactive glass nanoparticles induced characteristic red emission originating from Eu emissions belonging to ⁵D₀–⁷F_J (J = 1–4) transitions and the strongest peak was at 612 nm (electric-dipole transition, ⁵D₀–⁷F₂). Color chromaticity coordinates confirmed emission in the red region. XPS spectrum revealed the existence of Eu and Zn dopant elements in 58S bioactive glass. After soaking characteristic peaks at 31.74° and 45.43° belonging to the hexagonal hydroxyapatite phase were detected in the XRD data, confirming the SEM images. 2% Eu doped SPION/Bioactive glass nanoparticles had the highest osteoblast viability up to 7 days in vitro, while doping the samples with 2% zinc did not yield bone cell viability as high as the Eu doped ones. Importantly, Eu doped SPION/Bioactive glass nanoparticles inhibited gram-positive Staphylococcus aureus (S. aureus) and gram-negative Escherichia coli (E. coli) growth up to 48 h in vitro. The results showed that Eu doping of SPION/Bioactive glass nanoparticles increased osteoblast viability and inhibited bacterial growth, while possessing superparamagnetic properties and exhibiting red luminescence.     

树枝状介孔生物活性玻璃的制备及其表征

摘要：以十六烷基三甲基溴化铵（CTAB）为模板剂，三乙醇胺（TEA）作为催化剂，正硅酸乙酯（TEOS）为硅源，四水硝酸钙（CaNT）为钙源，磷酸三乙酯（TEP）为磷源，采用溶胶-凝胶法在不同温度下（40 ℃、60 ℃、80 ℃）制备树枝状介孔生物活性玻璃RMBG1、RNBG2、RNBG3，最后采用高温煅烧的方法除去模板。通过场发射扫描电镜(FESEM)、透射电子显微镜(TEM)、全自动快速比表面积与空隙度分析仪（BET）、纳米粒度分析仪(ZS)表征在不同反应温度下树枝状生物活性玻璃的形貌、结构、粒径和稳定性。结果表明：在60 ℃时所制备的树枝状介孔生物活性玻璃RMBG2粒径均一、分散性好、比表面积大，具有三维开放的树枝状孔道的独特结构优势。X射线电子能谱定性分析表明RMBG2中含有Si、Ca、P三种元素，等离子体光谱仪（ICP）表明RMBG2各元素对应的摩尔比大致为Si：Ca：P=84：14：2。RMBG2的比表面积高达821.161 m2g-1,孔径为孔体积为3.184 m3.g-1,可作为高效的药物载体。     

Characterization,in vitro bioactivity and biological studies of sol-gel-derived TiO2 substituted 58S bioactive glass

Bioactive glasses (BGs) have been used for bone formation and bone repair processes in recent years. This study investigated the titanium substitution effect on 58S BGs (Ti-BGs) 60SiO₂-(36 − X)CaO-4P₂O₅-XTiO₂ (X = 0, 3, and 5 mol.%) prepared by the sol-gel technique, and the main goal was to find the optimum amount of titanium in Ti-BGs. Synthesized BGs, which were investigated after immersion in simulated body fluid (SBF), were tested by X-ray diffraction (XRD) analysis, Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy. Moreover alkaline phosphate (ALP) activity, 3-(4,5dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay, and antibacterial studies were employed to investigate the biological properties of Ti-BGs. According to the FTIR and XRD test results, hydroxyapatite (HA) formation on Ti-BGs surfaces was confirmed. Meanwhile, the presence of 5 mol.% compared to 3 mol.% increased the HA grain distribution and their size on the Ti-BGs surface. Additionally, MTT and ALP results confirmed that the optimal amount of titanium substitution in BG was 5 mol.%. Since 5 mol.% Ti incorporated BG (BG-5) had the highest biocompatibility level, antibacterial properties, maximum cell proliferation, and ALP activity among the synthesized Ti-BGs, it is presented as the best candidate for further in vivo investigations.     

Effect of S53P4 bioactive glass content on structural and in-vitro behavior of hydroxyapatite/bioactive glass mixtures prepared by mechanical milling

This work presents silicon-substituted hydroxyapatite preparation through planetary ball milling using biogenic hydroxyapatite and different wt% of S53P4 bioactive glass (5, 10, 15, and 20 wt%) sources for the first time. The prepared mixtures showed a BHAp lattice contraction with SiO₄^4? incorporation; rich- and poor-Si phases were subsequently identified. Furthermore, two types of interaction among the functional groups in the S53P4 and BHAp mixtures are proposed. First, the 95-5 (wt.%) sample displayed a BHAp lattice with SiO₄^4?, CO₃^2?, and OH^? ions substitution. In samples with S53P4 BG content higher than 95-5, the lattice substitution was related to SiO₄^4?, PO₄^3?, and CO₃^2? ions, and a dehydroxylation process occurred in the BHAp. Finally, the bioactive behavior of the samples was studied by immersion in Hank's solution for 7, 14, and 28 days. The results showed that the mixtures formed a bone-like apatite layer with a dune-like morphology that increased in size and quantity with increasing S53P4 content in the mixtures.     

Preparation and properties of ferromagnetic glass ceramics and glass fibers based on the composition of SiO2-B2O3-Fe2O3-SrO

The ferromagnetic glass ceramics in the system SiO₂-B₂O₃-Fe₂O₃-SrO were prepared via four different fabrication methods, i.e., fiber-drawing, melt-quenching, natural-cooling, and annealing, without performing any nucleation and crystallization heat treatments. The influences of chemical composition and fabrication method on the spontaneous crystallization of magnetite were investigated by X-ray diffraction, scanning and transmission electron microscopy. The X-ray diffraction patterns show the presence of nanometric magnetite crystals in the glass matrix, and the increasing boron oxide can promote the spontaneous crystallization of magnetite. The estimated size of crystallized magnetite varies between 12 and 50 nm. The magnetic properties of the glass ceramics derived from the four fabrication methods were analyzed using a Vibrating sample magnetometer (VSM), Agilent HP8722ES vector network analyzer and Mössbauer spectra. We find that both the saturation magnetization (M_S) and coercivity (H_jc) depend on the chemical composition and fabrication method. The calorimetric measurements were carried out using Orton Standard Dilatometers.     

Facile fabrication of hollow mesoporous bioactive glass spheres: From structural behaviour to in vitro biology evaluation

Bone defects accompanied by infection or inflammation can significantly delay the healing process. To simultaneously achieve controlled release of local antibiotics for infection control and bone healing, bone-implantable delivery systems have been considered as a promising strategy. This study aims to improve drug loading capacity of bone-implantable delivery systems by introducing hollow structure mesoporous bioactive glass nanospheres (HMBGs) through a sol–gel process. Particularly, such core–shell bimodal-porous structured nanoparticles were prepared through a sacrificing template using cetyltrimethylammonium bromide (CTAB) as surfactant. It was found that varying the amount of CTAB during the synthesis process is a simple and effective approach for tuning the particle size, morphology, and structure of HMBGs. For in vitro drug release, HMBGs could sustain storage and release of vancomycin hydrochloride (VAN) via diffusion-controlled mechanism, thereby inhibiting the bacteria growth in the subsequent bacterial study. Moreover, HMBGs incorporated with VAN provided a biomimetic microenvironment favored by cell adhesion and proliferation. These findings support the compatibility of HMBG nanoparticles with antibiotics and their potential application in the treatment of infectious bone defects.     

Synthesis,characterization, bioactivity and cytotoxicity assessment of nano ZrO2 reinforced bioactive glass ceramics

Bioactive glass and glass ceramics have travelled a long way as biomaterials. Several research works have been devoted to improving mechanical properties, especially using various additives. Out of these, ZrO₂-containing glass and glass ceramics have shown promising outcomes. In this present work, a set of 3 Nano-ZrO₂ containing novel bioactive glass and glass ceramics of composition 37.5 nano-SiO₂–(17-X)Al₂O₃–26.5CaO–11.5CaF₂–7.5P₂O₅–X nano-ZrO₂ (where, X= 0.75, 1.7, 2.7, all in mol %) were synthesized by melt-quenching technique. Standard characterization procedures were performed to assess the physical and chemical properties, structure and surface morphologies. In vitro bioactivity and cytotoxicity assessments were also done. Fluorapatite (Ca₅(PO4)₃F) and Anorthite (Ca(Al₂Si₂O₈)) along with tetragonal Zirconia (t-ZrO₂) at higher nano-ZrO₂ content of 2.7 mol% were discovered as the primary crystalline phases. Adding nano-zirconia enhanced the glasses' thermal stability and the glass ceramics' micro-hardness. The formation of nanometer-size hydroxyapatite (HAp) on the glass-ceramics samples confirmed the good bioactive nature. The non-toxic nature of the samples towards living cells was demonstrated by cytotoxicity assessment.